Molybdenum disilicide composites

ABSTRACT

Molybdenum disilicide/β′-Si 6-z Al z O z N 8-z , wherein z=a number from greater than 0 to about 5, composites are made by use of in situ reactions among α-silicon nitride, molybdenum disilicide, and aluminum. Molybdenum disilicide within a molybdenum disilicide/β′-Si 6-z Al z O z N 8-z  eutectoid matrix is the resulting microstructure when the invention method is employed.

This application claims the benefit of U.S. Provisional Application Ser. No. 60/048,042, filed May 30, 1997.

This invention was made with government support under Contract No. W-7405-ENG-36 awarded by the U.S. Department of Energy. The government has certain rights in the invention.

TECHNICAL FIELD

This invention relates to structural suicides and more particularly to molybdenum-based silicides and eutectoid composites thereof.

BACKGROUND ART

Structural suicides have important high temperature applications in oxidizing and aggressive environments. There is a continuing and growing need for these materials for applications such as furnace heating elements, molten metal lances, industrial gas burners, aerospace turbine engine components, diesel engine glow plugs and materials for glass processing.

Some of the materials which would theoretically meet some of these needs are difficult to make and/or have deficiencies in engineering properties. For example, conventionalβ′-SiAlON is produced using silicon, aluminum nitride, and alumina in a nitrogen atmosphere. Due to impurities, β′-SiAlON is normally difficult to produce in a useful structural form according to such sources as the Encyclopedia of Materials Science and Engineering.

Therefore, it is an object of this invention to provide structural silicides with advantageous engineering properties.

It is another object of this invention to provide a method of making structural silicides with advantageous engineering properties.

It is a further object of this invention to provide molybdenum-based silicides.

It is yet another object of this invention to provide a method of making molybdenum-based silicides having improved purity.

It is an object of this invention to provide eutectoid composites of structural silicides having improved purity.

It is another object of this invention to provide a method of making eutectoid composites of structural suicides having improved purity.

Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims. The claims appended hereto are intended to cover all changes and modifications within the spirit and scope thereof.

DISCLOSURE OF INVENTION

To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein, there has been invented a composition comprising β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, within a molybdenum disilicide matrix.

There has been invented a novel method for making structural disilicides comprising:

(a) combining a major portion of molybdenum disilicide with a minor portion of silicon nitride and a minor portion of aluminum in an inert atmosphere to form a mixture;

(b) forming the mixture into desired shape;

(c) sintering the shape to form a composite of β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, in a molybdenum disilicide matrix.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures, which are incorporated in and form a part of the specification, illustrate embodiments of the present invention and, together with the description, serve to explain the principles of the invention. In the figures:

FIG. 1 is a graph of an example of a typical firing and sintering schedule used in the practice of the invention method.

FIG. 2 is an X-ray diffraction pattern of a composite made in accordance with the invention method.

FIG. 3 is a scanning electron image of the microstructure of an eutectoid matrix region of a composite made in accordance with the invention method.

FIGS. 4a and 4 b are elemental mappings of the same area of the microstructure of the composite shown in FIG. 3.

FIG. 4a is an elemental mapping of Mo K_(α) and

FIG. 4b is an elemental mapping of Al K_(α).

FIG. 5 is scanning electron micrograph image of a eutectoid matrix region of a composite made in accordance with the invention method.

FIG. 6 is a Si K_(α) mapping of the same area of the eutectoid matrix region of the composite shown in FIG. 5.

FIG. 7 is a lower magnification scanning electron micrograph image of a eutectoid matrix region made in accordance with the invention method.

FIG. 8 is a Si K_(α) mapping of the same area of the eutectoid matrix region of the composite shown in FIG. 7.

BEST MODES FOR CARRYING OUT THE INVENTION

It has been discovered that molybdenum disilicide/β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, eutectoid composites can be made by use of in situ reactions among α-silicon nitride, molybdenum disilicide, silicon dioxide, aluminum oxide, and aluminum. β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, within a molybdenum disilicide/β′-Si_(6-z)Al_(z)O_(z)N_(8-z) eutectoid matrix is the resulting microstructure when the invention method is employed.

The invention method comprises combining a major portion of molybdenum disilicide powder with a minor portion of silicon nitride powder to form a mixture which is then combined with a minor portion of aluminum powder with alumina coating on the aluminum particles. Alternatively, all three components can be combined simultaneously rather than sequentially. The resulting tripartite mixture is dried and de-agglomerated as needed, cold pressed or slip cast, then fired and sintered to form the eutectoid composite of this invention.

In the invention method, both alumina and aluminum nitride are produced in situ in the molybdenum disilicide matrix material followed by an in situ production of β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, at a temperature above 1400° C. These in situ reactions result in a pure β′-Si_(6-z)Al_(z)O_(z)N_(8-z) within a eutectoid microstructure.

Molybdenum disilicides which are useful in the practice of the invention are those with a high degree of purity, with only very minor amounts of silicon dioxide or having only impurities which would not affect the properties of the sintered product. Generally molybdenum disilicides without any Mo₅Si₃ are preferred.

An amount of molybdenum disilicide sufficient to impart thermal conductivity and other desired physical properties is needed; thus an amount of molybdenum disilicide sufficient to form the continuous phase is necessary. An amount in the range from about 55 weight percent to about 95 weight percent, based upon total weight of the matrix and reinforcing material, is generally useful in the invention. More preferable is an amount of molybdenum disilicide in the range from about 65 to about 90 weight percent, based upon total weight of the matrix and reinforcing material. Generally presently most preferred is an amount of molybdenum disilicide in the range from about 75 to about 85 weight percent.

Use of too little molybdenum disilicide will result in failure to form a eutectoid structure and unsintered Si₃N₄ in the end product and dissociation of the final product. Use of too much molybdenum disilicide will cause inferior properties in the resulting product.

An amount of silicon nitride sufficient to provide structural integrity to the end product is needed. An amount in the range from about 10 weight percent to about 25 weight percent, based upon total weight of the composition, is generally useful in the invention. More preferable is an amount of silicon nitride in the range from about 15 to about 20 weight percent, based upon total weight of the composition. Generally presently preferred is an amount of silicon nitride in the range from about 16 weight percent to about 18 weight percent, based upon total weight of the composition.

β′-Si_(6-z)Al_(z)O_(z)N_(8-z) will not form if too little silicon nitride is used. Use of too much silicon nitride will cause an insufficiently reinforced eutectoid matrix.

Aluminum which is useful in the practice of the invention is that which is in powder form and which can easily be coated with the alumina. An amount of aluminum sufficient to cause an ion displacement on the Si₃N₄ structure is needed. An amount of aluminum in the range from about greater than 0 to about 15 weight percent, based upon total weight of the composition, is generally useful in the invention. More preferable is an amount of aluminum in the range from about 1 weight percent to about 10 weight percent, based upon total weight of the composition. Generally presently preferred is an amount of aluminum in the range from about 3 weight percent to about 5 weight percent, based upon total weight of the composition.

Use of too little aluminum would result in less than the desired amount of alumina. Use of too much aluminum would likely cause distortion in the product.

Minor amounts of additives can be used as desired for various reasons. Additives can be used for improving the sinterability of the silicon nitride. For example, an additive such as yittrium aluminum garnet will cause a liquid phase to exist when the silicon nitride is just beginning to densify, with the liquid phase increasing the speed of the densification so that the silicon nitride densifies at a lower temperature. Use of too much yittrium aluminum garnet as an additive can cause decreases in fracture toughness and strength of the eutectoid composite. If sufficient amounts of the eutectoid are formed, the adverse effects of such additives would be negligible.

The silicon nitride can be combined with the molybdenum disilicide and ball milled prior to addition of the aluminum, or the silicon nitride can be combined with the aluminum and ball milled prior to combining the silicon nitride/aluminum mixture with the molybdenum disilicide, or the three components can be simultaneously combined and ball milled. It is generally presently preferred to mix the three components simultaneously to reduce risk of contamination.

The combining and subsequent mixing of the components is carried out in an inert atmosphere. Nitrogen gas is the presently preferred atmosphere.

Wet or dry ball milling or mixing by any other convenient means can be used. The mixture of components is ball milled, or otherwise mixed for a time sufficient to produce a uniform mixture of uniformly sized particles. Generally, ball milling the mixture for approximately 6 to 12 hours will accomplish a uniform distribution of particles sizes.

After complete mixing and milling of the three components, the ball-milled mixture can then be dried if needed. The dried cake can be crushed with a mortar and pestle or broken up by any other suitable means as needed to obtain a fine powder for subsequent ball milling with the third component, if the components are added sequentially or for subsequent ball milling with any additives used.

The mixture of ball milled, dried and powdered components can be processed in accordance with green body forming techniques such as slip casting, complex shape forming techniques, or, usually, it is then cold pressed or otherwise processed into pellets or whatever shapes are desired. Slip or compacted molds can be used.

The cold pressed pellets are first heated in a high vacuum and nitrogen atmosphere to decrease the possibility of unwanted oxidation during processing. It is essential that the pellets are first heated to a temperature above 550° C.; generally the maximum temperature should be from about 700° C. to about 800° C. At the maximum temperature the mixed, shaped components are divested of any combustible contamination and any interparticle moisture.

With the nitrogen atmosphere continued at positive pressure, the temperature is then held at a temperature in the range from about 500° C. to about 700° C. for long enough to accomplish burning out of all organic materials which may be in the pellets. Generally this will be about 10 minutes or so.

After burnout of the organic material from the pellets, the temperature is ramped up to a temperature of at least 1400° C. over a period of time, generally about two hours or so. Generally, a temperature increase of no more than 5° C. to 20° C. per minute is required because ramping the temperature up too quickly may cause entrapment of evoled gases and or cracking. More rapid ramping up of the temperature is feasible if the components have been dry milled. Ramping the temperature up too slowly could promote undesirable oxidation and would be economically infeasible.

A peak temperature of at least 1400° C. is needed for about 5 hours. Generally, peak temperatures in the range from about 1500° C. to about 1700° C. are preferred. The pellets should be sintered, still in a nitrogen atmosphere, at the peak temperature long enough for sintering of the molybdenum disilicide so that single phase molybdenum disilicide will be in the MoSi₂-B′-Si_(6-z)Al_(z)O_(z)N_(8-z) eutectoid matrix. Generally this will be a period from about ½ hour to about 5 hours, depending upon nitrogen pressure and sample composition. The larger the amount of silicon nitride, the greater the need for sintering. Lower temperatures may be needed if additives are used. Heating at a high peak temperature for too long a period can cause the materials to settle out, forming a graded or layered composite have a mostly eutectoid bottom layer and mostly molybdenum disilicide top layer. Heating at the peak temperature for too short a period will result in incomplete sintering.

After sintering at the peak temperature for the selected period of time, the temperature is decreased at a rate not to exceed about 15° C. per minute until a cooled temperature is reached.

Table 1 shows results of test runs of comparative compositions (Runs 1-21) and of an invention composition (Run 22) using varying temperatures, atmospheres, and components.

Because the compositions of this invention are sintered without hot pressing, the invention method can be used to create materials of unusual or irregular shapes. The invention method also avoids the economic disadvantages of hot pressing processes.

The composites of this invention have desirable physical properties such as: a melting point above 1800° C., high oxidation resistance, high thermal and electrical conductivity, excellent sinterability, relatively low density, high purity, and very high hardness. The composites of this invention have relatively low coefficients of thermal expansion, and thus have increased resistance to thermal shock. The composites of this invention can be easily machined into desired shapes.

The following examples will demonstrate the operability of the invention.

EXAMPLE I

Operability of the invention method was demonstrated by making a molybdenum disilicide/β-SiAlON, wherein z=a number from greater than 0 to about 5, eutectoid composite from molybdenum disilicide powder and α-Si₃N₄ powder. The molybdenum disilicide Grade C powder commercially available from H. C. Starck and α-Si₃N₄ powder commercially available as UBE SN-E-10 was used in each of the samples.

The molybdenum disilicide and Si₃N₄ powders were first mixed in volume ratios of 70:30, 80:20, 90:10, and 100:0. Respective weight ratios were 82.2:17.8, 88.8:11.2, 94.7:5.3, and 100:0. To prepare the mixtures, each powder was weighed (±0.01 grams) and then poured into a polyethylene ball mill container.

Two sizes of zirconia ball media were placed about ¼ full. For wet mill mixing efficiency, acetone was added. Each mixture was then ball milled for at least 4 hours.

After ball milling, each mixture was dried at 35° C. for 4 to 6 hours. The dry residue was then scraped and ground in an alumina bowl with an alumina pestle with minimal crushing force. The fine powder was then collected and stored in sealed containers.

To the 80:20 volume mixture of MoSi₂/Si₃N₄, a 3.8 weight percent aluminum additive was added by the same method as the initial mixture preparation. The resulting composition was 85.4 weight % MoSi₂, 10.8 weight % α-Si₃N₄, and 3.8 weight % fine aluminum. The container was then ball milled for 12 hours.

The powders of each mixture were then cold pressed at about 140 MPa in a stainless steel die. Resulting pellet dimensions were: 1.27 cm (±0.005 cm) outside diameter with thicknesses ranging from 0.17 to 0.22 cm (±0.005 cm). The starting masses ranged from 0.6 to 0.8 grams (±0.001 g).

The cold pressed pellets were then placed within a graphite crucible and covered with another crucible, with sufficient ventiliation. The crucibles containing the pellets were then placed in a high temperature Astro vacuum furnace.

Each of the samples was then sintered according to the sintering schedule shown in FIG. 1. The crucibles were heated slowly at a rate of 5 to 10° C. per minute to about 450° C. in a high vacuum. At this temperature the furnace was filled with nitrogen until a slight positive gas flow was achieved (about 5 to 10 kPa). The temperature was increased and held at approximately 550° C. for 10 minutes for organic matter bum-out. The heating rate was then resumed until the sintering temperature was reached. Various ones of the samples were sintered at 1500° C., 1600° C., 1650° C. and 1700° C. using times of 1, 2 and 3 hours. Cooling was done at the same rate as the heating rate. The MoSi₂/β′-SiAlON euctectoid composite sample appeared to sinter in a uniform manner without distortion. Also, there was much less volume shrinkage (68% original volume for this specimen while 53% original volume for a 100% MoSi₂ sample- with similar densification at the same time and temperature). Less volume shrinkage without distortion is an important feature because of the consequential lower density, better dimensional tolerance, and less mold fabrication difficulties. The overall density for an 80-20 MoSi₂—Si₃N₄ volume percent composition was 5.68 g/cm³ compared to an estimated theoretical density of 5.45 g/cm³ for the invention composition.

After sintering, the samples were weighed to determine any losses. The densities were calculated by water submersion methods as described in Pennings and Greliner, “Precise Nondestructive Determination of the Density of Porous Ceramics,” Journal of the American Ceramics Society, 75[8](1992)2056-2065. X-ray diffraction analysis and elemental mapping by EDS in SEM were done. Hardness and indentation fracture was determined by the Vickers microhardness indentation test, using a 1 kg load for 25 seconds.

Results of tests of physical properties of the invention eutectoid matrix are shown in Table 1.

TABLE 1 Properties of the MoSi₂/β′-Si_(6-z)Al_(z)O_(z)N_(8-z) Eutectoid Matrix Composition by volume % 70% MoSi₂ 30% β′-Si_(6-z)Al_(z)O_(z)N_(8-z) Composition by weight % 82% MoSi₂ 18% β′-Si_(6-z)Al_(z)O_(z)N_(8-z) Theoretical density 5.16 g/cm³ Sinterability (at 1700° C. for 3 hours) >99% dense Vickers Hardness 12.9 GPa

X-ray diffraction and elemental mapping on polished specimens provided the composition of each sample.

Quantitative microstructural analysis on the phases present was done on a scanning electron micrograph.

The X-ray diffraction pattern of the composite is shown in FIG. 2. MoSi₂, β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, and a small amount of Mo₅Si₃ was present in each of the samples.

The microstructure of the composite is shown in FIG. 3, while elemental mappings by energy dispersion analysis of Mo K_(α) and Al K_(α) are shown in FIGS. 4a and 4 b.

FIGS. 5 and 6 show a scanning electron micrograph image of the eutectoid matrix region and the Si K_(α) mapping of the same area. The presence of silica can be noted throughout the sample.

FIGS. 7 and 8 show a lower magnification scanning electron micrograph image and the Al K_(α) mapping. In this image it can be noted that Al is concentrated within a matrix dark phase (indicating β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5.

EXAMPLE II

Twenty-two sets of runs were made which show comparison of the inventive composition (Runs 22-1 through 22-5) with other compositions and sintering schedules. These comparison runs and the results are shown in Tables 2 and 3.

TABLE 2 Sintering of MoSi₂—Si₃N₄ Composi- tion, (volume %) Temperature, MoSi₂/ Time, Run Si₃N₄ Atmosphere Sinter bed Results  1-1 100/0  1 hr, 3 hr at none 85% dense,  1-2 90/10 1700° C.; grain size increase with  1-3 80/20 3 hr at Si₃N₄ content, 1600° C. green precipitate.  1-4 70/30 Argon  2-1 70/30 1 hr at 100% 90 ± 2% dense with sealed 1700° C. MoSi₂ surface cracks.  2-2 100/0  Argon  3-1 80/20 1 hr at 75-85% density, dark 1700° C. color, distorted,  3-2 100/0  Nitrogen none ellipsoidal shape, SiC precipitates.  4-1 80/20 1 hr at 100% Non-distorted but 1600° C. Si₃N₄ unsintered, crackfree  4-2 100/0  Nitrogen surfaces.  5-1 70/30 3 hr at 100% highly sintered, dense, 1700° C. Si₃N₄ greenish SiC precipitate.  5-2 80/20 Argon  5-3 100/0   6-1 70/30 3 hr at 100% BN highly sintered, dense,  6-2 80/20 1700° C. SiC precipitate.  6-3 100/0  Argon  7-1 80/20 3 hr at 100% BN sintered, low density,  7-2 100/0  1600° C. Al₂O₃ samples appeared darker. Nitrogen plate  8-1 80/20 3 hr at 50/50% slightly sintered, low  8-2 100/0  1700° C. MoSi₂/ density, SiC precipitate on  8-3 70/30 Nitrogen Si₃N₄ samples and crucible.  8-4 90/10  9-1 80/20 3 hr at 50/50% sintered, distorted,  9-2 100/0  1700° C. MoSi₂/BN dark gray color, Nitrogen SiC precipitate. 10-1 100/0  1 hr at 67/33 unsintered, dark gray color, 10-2 90/10 1700° C. BN/Si₃N₄ SiC precipitate, 10-3 80/20 Nitrogen 20/80 sample triple size, 10-4 70/30 very unsintered. 10-5 50/50 10-6 20/80 11-1 100/0  3 hr at 3SiO₂ + 70/30 sample unsintered; 11-2 90/10 1700° C. Si₃N₄ 80/20, 90/10, 100/0  11-3 80/20 Nitrogen in BN samples partially sintered. 11-4 70/30 11-5 20/80 12-1 100/0  3 hr at 3SiO₂ + all unsintered, SiC 12-2 80/20 1500° C. Si₃N₄ precipitate, very light color. 12-3 70/30 Nitrogen in BN 13-1 100/0  3 hr at SiO₂ + all samples unsintered. 13-2 80/20 1600° C. Si₃N₄ Nitrogen in BN 14-1 100/0  3 hr at SiO₂ + all unsintered and very low 14-2 80/20 1600° C. Si₃N₄ density. 14-3 80/20 + Nitrogen in BN 1 wt % SiO₂ 14-4 80/20 + 5 wt % SiO₂ 15-1 80/20 3 hr at MoSi₂ all sintered, estimated 85% 15-2 80/20 + 1600° C. theoretical density. 5 wt % Argon SiO₂ 16-1 80/20 3 hr at SiO₂ + well sintered, 16-2 80/20 + 1600° C. Si₃N₄ extensive cracking. 5 wt % Argon in BN SiO₂ 17-1 80/20 3 hr at none well sintered. 17-2 80/20 + 1600° C. 5 wt % Argon SiO₂ 18-1 100/0  3 hr at α-Si₃N₄ all samples except 100/0 18-2 80/20 1700° C. failed to sinter; possible 18-3 80/20 + Nitrogen error in atmosphere control. 4 wt % Al₂O₃ 18-4 80/20 + 4 wt % Al 19-1 100/0  3 hr at none all samples well sintered, 19-2 80/20 1600° C. 19-3 sample sintered but 19-3 80/20 + Argon had cold press cracks. 4 wt % Al₂O₃ 19-4 80/20 + 2 wt % C 19-5 100/0 + 2 wt % C 20-1 100/0  3 hr at 70/30 all samples well sintered, 20-2 80/20 1600° C. wt % 80/20 + 2C sample sintered 20-3 80/20 + 2 Argon MoSi₂/ but had cold press cracks. wt % C SiC 20-4 100/0 + 2 wt % C 20-5 80/20 + 4 wt % Al₂O₃ 21-1 100/0  3 hr at 70/30 all sintered well; 21-4 had 21-2 80/20 1700° C. wt % many cracks along grains; 21-3 80/20 + Nitrogen MoSi₂/ 21-5 split it in two by 2 wt % C SiC cracking. 21-4 80/20 + 4 wt % Al₂O₃ 21-5 80/20 + 4 wt % Al 22-1 100/0  3 hr at 100% 100/0, 80/20, 80/20 + 4Al 22-2 80/20 1700° C. α-Si₃N₄ all sintered well; 80-20 22-3 80/20 + Nitrogen distorted; 80/20 + Al 2 wt % C extremely brittle; 80/20 + 22-4 80/20 + C cracked due to distortion. 4 wt % Al₂O₃ 22-5 80/20 + 4 wt % Al

TABLE 3 Sintering of MoSi₂—Si₃N₄ MoSi₂/Si₃N₄ (vol %); X-ray Weight Loss or Gain Diffraction Run (wt %) Analysis Comments 1-1 100/0; none 1-2, 1-3, 1-4: no Silicon nitride 1-2 90/10; 2.5-3% loss Si₃N₄, all decomposition 1-3 80/20; 10-11% loss MoSi₂; occurring, SiO gas 1-4 70/30; 16-18% loss SiC precipitate likely to react w/graphite crucible producing SiC precipitate. 2-1 100/0 ; none 2-1, 2-2: no Silicon nitride 2-2 70/30; 15% loss Si₃N₄, all decomposition MoSi₂; occurring, SiO gas SiC precipitate likely to react w/graphite crucible producing SiC precipitate; embedding powder improved quality of sintered product. 3-1 100/0; 7% loss no X-ray results; MoSi₂ likely went 3-2 80/20; 16% loss samples appear through a structure same as Runs change, large amount 2-1, 2-2 of SiC indicates silicon nitride decomposition. 4-1 100/0; 8% gain 4-1: Mo₅Si₃ + Molydisilicide and 4-2 80/20; 8% gain β-Si₃N₄ alpha-silicon nitride go through structure change. 5-1 100/0; none 5-2: 100% MoSi₂; MoSi₂ transforrnation 5-2 80/20; 8% loss SiC precipitate appears affected by 5-3 70/30; 13% loss argon (rather than nitrogen) atmosphere. 6-1 100/0; none 6-2, 6-3: Although greater 6-2 80/20; 18% loss 100% MoSi₂ weight losses than in 6-3 70/30; 17% loss Runs 1-5, essentially same results. 7-1 80/20; 7% gain 7-1: tetragonal Both MoSi₂ and 7-2 100/0; 7% gain Mo₅Si₃; α-Si₃N₄ structure large amount changes: MoSi₂ => β-Si₃N₄ Mo₅Si₃ + 7Si 7Si + xN₂ => β-Si₃N₄. 8-1 80/20; 2% loss 8-1: MoSi₂ Thermodynamic 8-2 100/0; less than 5% and hexagonal coexistance of β-Si₃N₄ 8-3 70/30; less than 5% Mo₅Si₃ and Mo₅Si₃; minimal 8-4 90/10; less than 5% coexist weight loss for all samples; hexagonal Mo₃Si₃ appears in equilibrium w/MoSi₂. 9-1 80/20; 13% loss 9-1: MoSi₂ All Si₃N₄ , 9-2 100/0; 3% loss some MoSi₂ lost. 10-1 80/20; about 13% loss 10-2: MoSi₂ 20-80 composition 10-2 20/80; about 35% gain 10-3: β-Si₃N₄ transforms to β-Si₃N₄ 10-3 and Mo₅Si₃ and Mo₅Si₃; weight 10-4 loss and gains 10-5 appeared to vary 10-6 linearly with Si₃N₄ content. 11-1 100/0; 5% loss 11-3: MoSi₂; Sintered α-Si₃N₄ is 11-2 90/10; 11% loss 11-4: tetragonal produced with reaction 11-3 80/20; 18% loss Mo₅Si₃ and mix. 11-4 rxn: α-Si₃N₄, 11-5 12-1 all gained about .1 g 12-2: tetragonal Tranformation to 12-2 Mo₅Si₃, and β-Si₃N₄ occurred at 12-3 large amount below 1500° C.; β-Si₃N₄ MoSi₂ to Mo₅Si₃ then back to MoSi₂ above 1600° C. 13-1 gains of 0.06 to 0.07% 13-2: tetragonal 13-2 Mo₅Si₃, and large amount β-Si₃N₄ 14-1 100/0; 10% gain 14-3 and 14-4: Inconclusive, since the 14-2 80/20; 2% gain tetragonal Mo₅Si₃ 100/0 sample also 14-3 80/20 + SiO₂; 7% gain and large amounts gained mass, need to 14-4 β-Si₃N₄ sinter in 100% Si₂N₄ or no bed for analysis. 15-1 80/20; 5% loss 15-2: only MoSi₂, Samples picked up 15-2 80/20 + SiO₂; although low MoSi₂ from embed- 10% loss weight losses ding powder. 16-1 80/20; 14% loss 16-2: MoSi₂ and SiO gas caused large 16-2 80/20 + SiO₂; SiC precipitate weight losses that 19% loss included Si₃N₄ and MoSi₃. 17-1 80/20; 8.4% loss 17-2: MoSi₂ and All SiO₂ additive 17-2 80/20 + SiO₂; SiC precipitate dissociated as in 13.8% loss Run 16. 18-1 See Results in Table 2. 18-2 18-3 18-4 19-1 100/0; <1% loss 19-1, 19-2, 19-3, Alumina additive 19-2 80/20; 9% loss 19-5: MoSi₂ seemed to have pre- 19-3 80/20 + Al₂O₃; 19-4: MoSi₂ and cipitated to the surface 8% loss SiC precipitate as mullite. No clear 19-4 80/20 + C; 10% loss evidence of Si₃N₄. 19-5 100/0 + C; 2.7% loss 20-1 100/0; <1% loss 20-1, 20-2, 20-3, Large weight losses in 20-2 80/20; >16% loss 20-5: MoSi₂ 80/20 and 80/20 with 20-3 80/20 + C; 13% loss 20-4: MoSi₂ and Al₂O₃ may include 20-4 80/20 + Al₂O₃; SiC precipitate MoSi₂ as well. MoSi₂/ >17% loss SiC bed clearly en- 20-5 100/0 + C; 3% loss hances sinterability of 80/20 + additive al- though not enough Si₃N₄. 21-1 100/0; 10% loss All samples were ex- 21-2 80/20; 13% loss tremely brittle. Mo₅Si₃ 21-3 80/20 + C; 12% loss coated MoSi₂ appears 21-4 80/20 + Al₂O₃; to be the result. 14% loss 21-5 80/20 + Al; 11% loss 22-1 100/0; 2% loss 80/20 + Al sam- Aluminum additive 22-2 80/20; 9% loss ple appears as eu- sample shows best 22-3 80/20 + C; 5% loss tectoid structure success. Possible to 22-4 80/20 + Al₂O₃; of MoSi₂ particles constrain tranforma- 16% loss w/in MoSi₂ tion to Mo₅Si₃ by 22-5 80/20 + Al; 2.6% loss β′/ carbon reacting with SiAlON lamella/ excess SiO₂ matrix 80/20 + C: MoSi₂, SiC, and β-Si₃N₄

While the compositions, processes and articles of manufacture of this invention have been described in detail for the purpose of illustration, the inventive compositions, processes and articles are not to be construed as limited thereby. This patent is intended to cover all changes and modifications within the spirit and scope thereof.

INDUSTRIAL APPLICABILITY

The eutectoid composites of this invention would be useful for structural components or heating elements because of high temperature resistance, high temperature electrical and thermal conductivity, and oxidation resistance properties. Electromachining of the invention material is greatly facilitated by the electrical conductivity. 

What is claimed is:
 1. A method comprising: (a) combining a major portion of molybdenum disilicide with a minor portion of silicon nitride and a minor portion of aluminum in an inert atmosphere to form a mixture; (b) forming said mixture into desired shape; (c) sintering said shape to form a composite of β′-Si_(6-z)Al_(z)O_(z)N_(8-z), wherein z=a number from greater than 0 to about 5, in a molybdenum disilicide matrix.
 2. A method as recited in claim 1 wherein said major portion of molybdenum disilicide, said minor portion of silicon nitride and said minor portion of aluminum are all combined contemporaneously.
 3. A method as recited in claim 1 wherein said major portion of molybdenum disilicide is first combined with said minor portion of silicon nitride to form a mixture which is then combined with said minor portion of aluminum.
 4. A method as recited in claim 1 wherein said aluminum is aluminum powder with alumina coating on the aluminum particles.
 5. A method as recited in claim 1 wherein said molybdenum disilicide contains no Mo₅Si₃.
 6. A method as recited in claim 1 wherein an amount of molybdenum disilicide sufficient to form a continuous phase is used.
 7. A method as recited in claim 1 wherein said molybdenum disilicide is present in an amount in the range from about 55 weight percent to about 95 weight percent, based upon total weight of the total composition formed.
 8. A method as recited in claim 1 wherein said molybdenum disilicide is present in an amount in the range from about 65 weight percent to about 90 weight percent, based upon total weight of the total composition formed.
 9. A method as recited in claim 1 wherein said molybdenum disilicide is present in an amount in the range from about 75 weight percent to about 85 weight percent, based upon total weight of the total composition formed.
 10. A method as recited in claim 1 wherein said silicon nitride is present in an amount sufficient to provide structural integrity to the resulting composition.
 11. A method as recited in claim 1 wherein said silicon nitride is present in an amount in the range from about 10 weight percent to about 25 weight percent, based upon total weight of the total composition formed.
 12. A method as recited in claim 1 wherein said silicon nitride is present in an amount in the range from about 15 weight percent to about 20 weight percent, based upon total weight of the total composition formed.
 13. A method as recited in claim 1 wherein said silicon nitride is present in an amount in the range from about 16 weight percent to about 18 weight percent, based upon total weight of the total composition formed.
 14. A method as recited in claim 1 wherein said aluminum is present in an amount sufficient to cause ion displacement of any Si₃N₄ structures formed.
 15. A method as recited in claim 1 wherein said aluminum is present in an amount in the range from greater than 0 weight percent to about 15 weight percent, based upon total weight of the total composition formed.
 16. A method as recited in claim 1 wherein said aluminum is present in an amount in the range from about 1 weight percent to about 10 weight percent, based upon total weight of the total composition formed.
 17. A method as recited in claim 1 wherein said aluminum is present in an amount in the range from about 3 weight percent to about 5 weight percent, based upon total weight of the total composition formed.
 18. A method as recited in claim 1 wherein said mixture is heated to a temperature above 550° C, then held at a temperature in the range from about 500° C. to about 800° C. for a time sufficient to bum substantially all organic materials present and thereafter heated at a peak temperature of at least 1400° C.
 19. A method as recited in claim 18 wherein said peak temperature is in the range from about 1500° C. to about 1700° C.
 20. A method as recited in claim 18 wherein said mixture is heated at said peak temperature for a time sufficient to form a molybdenum disilicide single phase in a MoSi₂/β′-Si_(6-z)Al_(z)O_(z)N_(8-z) eutectoid matrix.
 21. A method as recited in claim 18 wherein said mixture is heated at said peak temperature for a period of time in the range from about one half hour to about 5 hours. 